JPH0211614B2 - - Google Patents
Info
- Publication number
- JPH0211614B2 JPH0211614B2 JP60094584A JP9458485A JPH0211614B2 JP H0211614 B2 JPH0211614 B2 JP H0211614B2 JP 60094584 A JP60094584 A JP 60094584A JP 9458485 A JP9458485 A JP 9458485A JP H0211614 B2 JPH0211614 B2 JP H0211614B2
- Authority
- JP
- Japan
- Prior art keywords
- thiophene
- polymer
- naphtho
- general formula
- dihydronaphtho
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 55
- QGGSWEDJFFDTIQ-UHFFFAOYSA-N benzo[f][2]benzothiole Chemical group C1=CC=CC2=CC3=CSC=C3C=C21 QGGSWEDJFFDTIQ-UHFFFAOYSA-N 0.000 claims description 20
- GJSDSQMOVFARPY-UHFFFAOYSA-N 1,3-dihydrobenzo[f][2]benzothiole Chemical compound C1=CC=C2C=C3CSCC3=CC2=C1 GJSDSQMOVFARPY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- AIIDQLCCKSININ-UHFFFAOYSA-N 1,3-dihydrobenzo[f][2]benzothiole 2-oxide Chemical compound C1=CC=C2C=C(CS(=O)C3)C3=CC2=C1 AIIDQLCCKSININ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920001197 polyacetylene Polymers 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical group C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000052 poly(p-xylylene) Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- -1 3-substituted dihydrothiophene Chemical class 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 241000282821 Hippopotamus Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 1
- KOXIVMUITVOLHH-UHFFFAOYSA-N chlorobenzene methylsulfinylmethane Chemical compound ClC1=CC=CC=C1.CS(=O)C KOXIVMUITVOLHH-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は極めて安定でドーピングにより極めて
高い電導性を示す新規な電導性重合体に関し、更
に詳しくは、くり返し単位として一般式
（式中、R1及びR2はそれぞれ独立に水素、炭
素数１〜５の炭化水素、メトキシ基及びメチルチ
オ基から選ばれた置換基を表わす）で表わされる
ナフト〔２，３―Ｃ〕チオフエン構造を有する重
合体の製造方法に関する。
この重合体は電気・電子工業の分野において電
極、エレクトロクロミツク表示素子、固体コンデ
ンサー、太陽電池等の製造に用いることができ
る。
〔従来の技術〕
近年、電気・電子機器の軽量化、薄形化或いは
小型化の進歩は著しく、それらに用いられる各種
素子等についても、軽量化、薄形化或いは小型化
への要望が強いばかりでなく、より優れた新規材
料の出現に強い期待が持たれている。これらの要
望或いは期待を満たすべく従来から新しい電導性
高分子の開発が盛んに行なわれている。例えば、
ポリアセチレンは、ヨウ素或いは五フツ化ヒ素な
どをドープすることにより、102〜103s／cmもの
高い電導度を示すこと〔例えばシンセテイツクメ
タルズ（Synthetic Metals）１(2)、101（1979／
1980）参照〕、充放電特性が優れていることから
二次電池の電極材料として検討されているばかり
でなく、光の吸収特性が太陽光のそれに近いこと
などの理由で太陽電池材料としても検討されてい
る。
しかしながら、ポリアセチレンは、それ自体酸
化され易く、またドープしたポリアセチレンは湿
気に対しても極めて敏感であるという欠点をもつ
ている。
一方ポリチオフエンは、その共役構造がシス型
ポリアセチレンに類似し、硫黄原子を含むという
その特異的な電子構造の故に、電導性材料として
或いは電池電極材料としての使用が検討されてい
るのみならず、エレクトロクロミツク材料として
の使用も検討されている。例えば、エー・エム・
ドルイ（A.M.Druy）等は、２，2′―ビチエニル
を電気化学的に重合して得られる重合体が、酸化
状態〜還元状態において、青色〜赤色と変色し、
この現象が可逆的であることを利用してエレクト
ロクロミツク材料として有用である旨報告してい
る〔ジエー・デ・フイジイクス（J.de Physique）
44(6)、C3―595（1983）参照〕。
〔発明が解決しようとする課題〕
本発明者らの一部は既に、イソチアナフテン構
造を有する重合体が空気中においても極めて安定
な化合物であり、繰り返し使用が十分可能な程、
安定に酸化又は還元状態への過程で可逆的に変色
し得るものであり、またドーピングにより、容易
に10-2s／cmより高い電導度を示すことを見出し
ている（特開昭61−17581号公報及び特開昭61−
12784号公報）。
本発明者らは、更に研究を進めた結果、上記イ
ソチアナフテン構造を有する重合体のベンゼン核
のπ共役系を更に拡張してナフテン核とすること
により、より低いエネルギーギヤツプを有する電
導性重合体とすることが可能であることを見出し
て本発明を達成した。
〔課題を解決するための手段及び作用〕
本発明に係る重合体は、くり返し単位として一
般式
（式中、R1及びR2はそれぞれ独立に水素、炭
素数１〜５の炭化水素、メトキシ基及びメチルチ
オ基から選ばれた置換基を表わす）で表わされる
ナフト〔２，３―Ｃ〕チオフエン構造を有するも
のであり、かかる重合体は以下の重合方法によつ
て合成することができる。
(1) 下記一般式
（式中、R1及びR2は前に定義した通り）で
表わされる、１，３―ジヒドロナフト〔２，３
―Ｃ〕チオフエン―２―オキシド及び／又はそ
の誘導体をポリリン酸のごとき溶媒中で脱水重
合させることにより、ポリ〔１，３―ジヒドロ
ナフト〔２，３―Ｃ〕チオフエン〕及び／又は
その誘導体とし、次いでこれを脱水素剤の作用
により所望のポリ〔１，３―ナフト〔２，３―
Ｃ〕チオフエン〕及び／又はその誘導体を製造
することができる。
(2) 前記一般式（ａ）で表わされる化合物を減
圧加熱下に脱水昇華させて得られる一般式
（式中、R1及びR2は前に定義した通り）で
表わされるナフト〔２，３―Ｃ〕チオフエン及
び／又はその誘導体を
(i) ラジカル重合開始剤、アニオン重合開始剤
又はカチオン重合開始剤を用いて重合させ、
得られるポリ〔１，３―ジヒドロナフト
（２，３―Ｃ）チオフエン〕及び／又はその
誘導体を(1)に記載の方法により脱水素するこ
とにより、所望の重合体とするか、
(ii) 一般式（ｂ）で表わされるナフト〔２，
３―Ｃ〕チオフエン及び／又はその誘導体を
溶媒及び電解質の存在下電気化学的に重合さ
せるか、或いは、
(iii) 一般式（ｂ）で表わされるナフト〔２，
３―Ｃ〕チオフエンをヨウ素又は無水塩化ア
ルミニウム及び塩化第一銅等の存在下に酸化
重合させて、ポリ〔１，３―ナフト〔２，３
―Ｃ〕チオフエン〕及び／又はその誘導体と
することができる。
前記一般式（ａ）又は（ｂ）で表わされる
単量体の重合に際して、用いられる重合条件はそ
れぞれの重合方法に応じた公知の方法に準じて設
定すればよく特に限定はない。
即ち、一般式（ｂ）で表わされる単量体を電
気化学的に重合する場合には、チオフエン、ピロ
ールなどを重合させるソリツド ステート コミ
ユニケーシヨン（Solid State Communication）
46(5)、389（1983）に記載の方法を応用することが
できる。この際、定電位法及び定電流法のいずれ
を用いてもよい。
また、液体ヨウ素中で、酸化重合させる場合に
各種置換又は非置換のカルバゾール化合物を重合
させるジエネエツケ（Jenekhe）らの方法、〔ポ
リマー物質のオーダーについてのシンポジウム
（Symposium on Order in Polymeric
Materials）、ウオルサム エムエー（Waltham
MA）８月25〜26（1983）〕を応用することができ
る。
また、無水塩化アルミニウム及び塩化第一銅に
より酸化重合させる場合にはベンゼンを重合させ
るコバシツク（Kovacic）らの方法〔マクロモ
ル．シン．（Macromol.Syn.２，23（1966）〕を応
用することができる。
更に得られたポリ〔１，３―ジヒドロナフト
〔２，３―Ｃ〕チオフエン〕及び／又はその誘導
体を脱水素して所望のポリ〔１，３―ナフト
〔２，３―Ｃ〕チオフエン〕及び／又はその誘導
体とするには溶媒の存在下又は不存在下にヨウ
素、臭素又はトリチルフルオロボレート、ジクロ
ロジシアノ―ｐ―ベンゾキノン、クロラニル、テ
トラシアノジメタンなどの脱水素剤を作用させる
ことにより容易に達成することができる。脱水素
反応に用いられる反応条件は、脱水素剤の種類溶
媒の有無などにより異なるため、一概に規定でき
ないが、アセトニトリル、クロルベンゼンなどを
用いた場合には、０℃〜溶媒の沸点の範囲で１時
間〜24時間で反応させればよい。脱水素剤の使用
量にポリ〔１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン〕及び／又はその誘導体の繰り返
し単位当り３倍モル〜20倍モルの範囲で用いられ
る。これら脱水素剤の作用による脱水素反応が十
分に行なわれない場合には、ジヒドロ体の構造が
重合体主鎖中に未反応のまま残ることにより共役
鎖が分断され、電導度の低下を招くおそれがある
ことから反応を十分に行なわしめることが必要で
ある。これらの方法で得られるポリ〔１，３―ジ
ヒドロナフト〔２，３―Ｃ〕チオフエン〕及び／
又はその誘導体は過剰の脱水素剤によりドーピン
グされたものとして得られ、必要に応じ、電気化
学的または化学的に容易にデドープすることがで
きる。化学的にデドープする方法としては重合体
をアンモニア又は三級アミン類のガスもしくは液
体に接触させることによつて容易に達成される。
電気化学的にデドープする方法としては金藤ら
〔ジヤパンジエー．オブ アプル．フイジイクス
（Japan J.of Appl.Physics）22(7)、L412（1983）〕
の方法に準じて行なえばよい。本発明に係る前記
一般式（ａ）で表わされる単量体化合物は、例
えばエム．ピー．カバ（M.P.Cava）等のジエ
ー．アム．ケム．ソク．（J.Am.Chem.Soc.）81，
4266（1959）及び同じくエム．ピー．カバ（M.P.
Cava）等のジエー．オルグ．ケム．（J.Org.
Chem.）36（25）、3932（1971）に記載の方法で合
成することができる。
〔発明の効果〕
前記したようにして得られた本発明に係る重合
体は、ドーピングにより極めて高い電導度を示す
ばかりでなく、電気化学的にも繰り返し酸化還元
を行なうことが可能で、かつそれぞれの状態にお
いて固有の色を有する。本発明のポリ〔１，３―
ナフト〔２，３―Ｃ〕チオフエン〕及び／又はそ
の誘導体は薄膜状態では酸化状態において無色透
明であるという極めて興味のある重合体である。
従つて本発明に係るポリ〔１，３―ナフト
〔２，３―Ｃ〕チオフエン〕及び／又はその誘導
体は電気・電子工業の分野において電極、エレク
トロクロミツク表示素子、固体コンデンサー、太
陽電池等の製造に極めて有用なものであることが
明らかである。
〔実施例〕
以下、実施例に従つて本発明を更に詳しく説明
する。なお、以下の実施例において重合体のIR
スペクトルは日本分光(株)製、Ａ―３型又は同社製
IRA―２型IRスペクトロホトメーターを用いて
測定し、1H―NMRスペクトルは、(株)日立製作所
製100MHzR―24B型高分解能NMRスペクトロ
メーターを用いて測定した。重合体の粘度は対数
粘度（ηinh）をもつて表示した。
なお、実施例中の粘度ηinhは次式により求めた
（式中、対数は自然対数を表わす）。
ηinh＝（１／Ｃ）ln（ｔ―to）／to
（式中、ｔ：重合体溶液の粘度計における標線
間の通過時間（秒）
to：純溶媒の粘度計の標線間の通過時間（秒）
Ｃ：重合体溶液の濃度（ｇ／100ml溶媒で表示）
実施例 １
(1) ポリ〔１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン〕の合成
(i) ポリリン酸中での１，３―ジヒドロナフト
〔２，３―Ｃ〕チオフエン―２―オキシドの脱
水重合
１，３―ジヒドロナフト〔２，３―Ｃ〕チオフ
エン―２―オキシド（一般式（ａ）でR1＝R2
＝Ｈ）2.38ｇ（11.8ミリモル）を窒素気流下100
℃に加熱した75％の五燐化リンを含むポリリン酸
25ｇ中に加え、４時間撹拌した後、反応液を１
の水中に注いだ。生成した沈澱を濾別、洗浄した
後、固体を５％希アンモニア水500ml中に入れ、
１時間撹拌し、濾別後、濾残を濾液や中性になる
まで十分水洗した後、メタノール、次いでアセト
ンで洗浄した。残渣を100℃で一夜真空乾燥し、
1.63ｇの淡褐色重合体を得た。
この重合体は、ジメチルスルホキシド クロル
ベンゼン、塩化メチレンに可溶であり、テトラヒ
ドロフラン、ジオキサンに一部可溶、メタノー
ル、アセトンに不溶であつた。重合体の0.5％の
ジメチルスルホキシド溶液中30℃における粘度は
ηinh＝0.102であつた。得られた重合体のIRスペ
クトルは第１図に示す通りであつた。また、テト
ラメチルシランを基準とした重合体の重水素化ジ
メチルスルホキシド溶液中の1H―NMRは７〜
8ppmにナフタレン環のプロトン、4.4ppmに１，
３―置換ジヒドロチオフエンのメチン基のプロト
ンのジクナルが表われ、そのプロトンの積分強度
比はほぼ６：２であつた。また元素分析値はＣ：
78.5％、Ｈ：4.35％（計算値はＣ：78.26％、Ｈ：
4.35％）であつた。
(ii) ナフト〔２，３―Ｃ〕チオフエンのカチオン
重合
１，３―ジヒドロナフトチオフエン―２―オキ
シド（一般式（ａ）でR1＝R2＝Ｈ）１ｇ（５
ミリモル）、中性アルミナ２ｇを乳鉢中で粉砕混
合し、昇華装置に充填した後、内筒部に冷却水を
通し、内部を20mmHgに保ちながら、外筒部を175
℃の油浴上に浸漬した。２時間後、内筒部のゴー
ルドフインガー部に昇華析出した黄色結晶を窒素
雰囲気下で別の昇華装置に移した後、再度室温に
て１mmHgの減圧下で脱水した。得られた450mg
（2.5ミリモル）のナフト〔２，３―Ｃ〕チオフエ
ンを予め水素化カルシウムで脱水蒸留した塩化メ
チレン５mlに溶解し、窒素雰囲気で−40℃に冷却
し、これに三フツ化ホウ素エーテラートの10容積
％の塩化メチレン溶液32μを加えた。溶液はた
だちに黒紫色になり、４時間後には粘稠な溶液と
なつた。重合を行なつている間の温度を−40℃に
保持した。その後、重合溶液に10％のトリエチル
アミンの塩化メチレン溶液１mlを加え重合を停止
させた。この時重合体溶液は黒紫色から淡褐色に
変化した。重合体溶液をメタノール100ml中に加
え、沈澱を生じさせた後、沈澱を濾別し、メタノ
ール、次いでアセトンで洗浄し、次いで一夜真空
乾燥し、380mgの黒褐色の重合体を得た。重合体
の0.5％のジメチルスルホキシド中30℃における
粘度はηinh＝0.156であつた。またIRスペクトル
は上記(i)で得られたものと完全に一致した。
(iii) ナフト〔２，３―Ｃ〕チオフエンのラジカル
重合
(ii)と同様にして１，３―ジヒドロナフト〔２，
３―Ｃ〕チオフエン―２―オキシド１ｇ（５ミリ
モル）を昇華脱水し、500mg（2.72ミリモル）の
ナフト〔２，３―Ｃ〕チオフエンを得た。これを
窒素置換した清浄な重合封管に入れ、５mlの精製
クロルベンゼン及び12mg（5.46×10-2ミリモル）
のアゾビスイソバレロニトリルを加え、ドライア
イス―エタノール浴に浸漬した後、真空脱気し
た。室温に戻した後、再冷却し、脱気した。この
操作を５回繰り返した後、真空下で重合封管を溶
封した。この封管を60℃で24時間重合させた。封
管を開封し、重合体のクロルベンゼンを100mlの
メタノール中に添加することにより重合体を沈澱
させ、次いで濾別し、アセトンで洗浄後、真空乾
燥して260mgの淡褐色重合体を得た。
得られた重合体の0.5％ジメチルスルホキシド
溶液中30℃における粘度はηinh＝0.07であつた。
このもののIRスペクトルは(i)で合成したものと
一致し、ポリ〔１，３―ジヒドロナフト〔２，３
―Ｃ〕チオフエン〕であることを確認した。
(iv) ナフト〔２，３―Ｃ〕チオフエンのアニオン
重合
(ii)と同様にして１，３―ジヒドロナフト〔２，
３―Ｃ〕チオフエン―２―オキシド２ｇ（9.9ミ
リモル）を昇華脱水し、1.06ｇ（5.76ミリモル）
のナフト〔２，３―Ｃ〕チオフエンを得た。これ
を磁気撹拌子、還流冷却器、温度計を付した50ml
の三つ口フラスコに入れ、窒素で内部を置換した
後、常法により水素化カルシウム上で脱水精製し
たテトラヒドロフラン10mlを加え、次いで、ｎ―
ブチルリチウムのｎ―ヘキサン溶液（濃度10％）
を0.2ml加え、撹拌しながら、60℃で24時間反応
させた。これを100mlのメタノールに加え、重合
体を沈澱させた後、別し、濾残を常法により洗
浄し、100℃で一夜真空乾燥し、淡褐色重合体
0.58ｇを得た。IRスペクトル(i)で合成したものと
一致し、ポリ〔１，３―ジヒドロナフト〔２，３
―Ｃ〕チオフエン〕であることを確認した。重合
体0.5％ジメチルスルホキシド溶液中30℃におけ
る粘度はηinh＝0.09であつた。
(2) ポリ〔１，３―ナフト〔２，３―Ｃ〕チオフ
エンの合成
(i) ポリ〔１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン〕のヨウ素酸化によるポリ
〔１，３―ナフト〔２，３―Ｃ〕チオフエン〕
の合成
(1)―(i)で得られたポリ〔１，３―ジヒドロナフ
ト〔２，３―Ｃ〕チオフエン〕１ｇ（5.43ミリモ
ル）を窒素下で25mlの精製クロルベンゼンに溶解
した後、6.90ｇ（27.2ミリモル）のヨウ素を加
え、４時間油浴上で還流させると、黒紫色の沈澱
が得られた。沈澱を濾別後、クロルベンゼン及び
メタノールでヨウ素の色が認められなくなるまで
十分洗浄した。次いで37％アンモニア水30mlとメ
タノール70mlからなる溶液に重合体を懸濁し、４
時間窒素下で加熱還流した後、沈澱を濾別してメ
タノールでよく洗浄し、次いで100℃で一夜真空
乾燥することにより、0.98ｇの黒緑色の重合体粉
末を得た。重合体のIRスペクトルを第２図に示
す。この重合体のバイルシユタイン反応は陰性で
あることからハロゲンは含まれていず、また元素
分析結果からはＣ：79.06％、Ｈ：3.40％（計算
値Ｃ：79.12％、Ｈ：3.30％）であつた。この重
合体は通常の有機溶媒には不溶であつた。更にこ
の重合体をITプレスでプレスしたペレツトの室
温における電導度σRTを４端子式の電導度測定器
を用いて測定したところσRT＝2.3×10-2s／cmであ
り、一夜ヨウ素蒸気に曝露したものの電導度は
σRT＝8.2×10-1s／cmであつた。ドープ後の重合体
は室温で１週間空気中に放置しても、その電導度
に変化はなかつた。
(ii) ポリ〔１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン〕の脱水素によるポリ〔１，３
―ナフト〔２，３―Ｃ〕チオフエン〕の合成
(1)―(i)の反応を繰り返して、ηinh＝0.117の重
合体1.5ｇを得た。この重合体１ｇを窒素気流下
20mlの精製アセトニトリルに溶解し、次いでこの
溶液にトリチルフルオロボレート8.97ｇ（27ミリ
モル）を加え、20℃で４時間反応させた。この間
重合体は淡褐色の均一溶液から反応の進行に伴
い、黒色の沈澱として溶媒から分離した。生成し
た沈澱を濾別後、アセトニトリルで十分洗浄し、
次いで濾残をクロロホルム30ml中に懸濁し、10％
のトリエチルアミンのクロロホルム溶液10mlを加
え、室温で一夜撹拌した。溶液から固体を濾別
し、100℃で一夜真空乾燥した。重合体のIRスペ
クトルは第２図に一致し、ポリ〔１，３―ナフト
〔２，３―Ｃ〕チオフエン〕であることを確認し
た。
実施例 ２
電気化学的重合法によるポリ〔１，３―ナフト
〔２，３―Ｃ〕チオフエン〕の合成
実施例１の(1)―(ii)に記載の方法で2.02ｇ（10ミ
リモル）の１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン―２―オキシド及び２ｇの中性ア
ルミナの混合物を脱水昇華させることにより1.06
ｇ（5.76ミリモル）のナフト〔２，３―Ｃ〕チオ
フエンを得た。このモノマーをガラスフイルター
付Ｈ型管に入れた150ミリモル／のテトラ―ｎ
―ブチルアンモニウムブロマイドのアセトニトリ
ル溶液20mlに溶解し、陰極に白金板、陽極に表面
抵抗値15Ω／□の酸化インジウム錫蒸着ガラス基
板を用い、電極間距離６cmで、北斗電機(株)製、定
電圧定電流発生装置（タイプHA―301型）を用
い、印刷電圧2.50の定電圧で50分間通電すること
により電気化学的重合を行なつた。電流値は重合
開始時は0.7mAであり、最大電流値は0.85mA、
重合終了時は0.49mAであつた。通電により陽極
上には濃青色フイルムが析出した。
実施例 ３
酸化重合法によるポリ〔１，３―ナフト〔２，
３―Ｃ〕チオフエン〕の合成
実施例１―(ii)に記載の方法で2.02ｇ（10ミリモ
ル）の１，３―ジヒドロナフト〔２，３―Ｃ〕チ
オフエン―２―オキシドおよび2.0ｇの中性アル
ミナの混合物を脱水昇華させることにより、0.91
ｇ（4.95ミリモル）のナフト―〔２，３―Ｃ〕チ
オフエンを得た。これをテトラヒドロフラン22ml
に溶解し、２，３―ジクロロ―５，６―ジシアノ
―１，４―ベンゾキノン1.18ｇ（5.2ミリモル）
を加え、窒素雰囲気下で室温で１時間、40℃で２
時間、還流温度で３時間反応させた。得られた沈
澱を濾別後20mlのメタノールで６回、50mlの0.2
規定カ性ソーダのメタノール溶液で１回、さらに
50mlのメタノールで３回洗浄し、次いで100℃で
１夜真空乾燥することにより、0.85ｇの黒緑色の
重合体粉末を得た。この重合体のIRスペクトル
は第２図に一致した。この重合体のバイルシユタ
イン反応は陰性であることからハロゲンは含まれ
ていず、また元素分析結果からはＣ：79.15％、
Ｈ：3.40％（計算値Ｃ：79.12％、Ｈ：3.30％）で
あつた。この重合体粉末をITプレスでプレスし
たペレツトの室温における電導度σRTを４端子式
の電導度測定器を用いて測定したところ、σRT＝
2.1×10-2s／cmであつた。
実施例 ４
本発明で得られたポリ〔１，３―ナフト〔２，
３―Ｃ〕チオフエン〕がエレクトロクロミツク表
示素子材料として有用であることを示す。
〔エレクトロクロミツク材料実験〕
実施例２で得たポリ〔ナフト〔２，３―Ｃ〕チ
オフエン〕で被覆された導電ガラスを負極に、白
金線を正極にして0.16モル／のリチウムパーク
ロレートのアセトニトリル溶液中で4.50Vの電圧
を印加したところ、重合体薄膜は濃青色から無色
に変化し、−1.5Vの電圧を逆印加すると無色から
濃青色に変化した。この変化は繰り返しの電圧印
加により可逆的に可能であり、エレクトロクロミ
ツク表示材料として有用であることを示した。
実施例 ５
本例は、本発明で得られたポリ〔１，３―ナフ
ト〔２，３―Ｃ〕チオフエン〕が固体コンデンサ
ー用材料として有用であることを示す。
厚さ100μｍのアルミ箔（純度99.99％）を陽極
として箔の表面を電気化学的にエツチングし、平
均細孔径2μｍで比表面積が12m2／ｇとした。つ
いでこのエツチング処理したアルミニウム箔にホ
ウ酸アンモニウムの液中で電気化学的に誘導体の
薄層を形成した。
実施例１の(1)―(i)の反応で得られたσinh＝
0.117の重合体0.2ｇを窒素気流下３mlの精製アセ
トニトリルに溶解させ、前記誘導体層に塗布し、
減圧脱気をくり返して充分細孔まで溶液を満たし
た後、アセトニトリルをドライアツプした。続い
てトリチルフルオロボレートのアセトニトリル溶
液（１モル／）中に浸漬し、20℃で20時間反応
させた。箔を取り出し、アセトニトリルで洗浄し
た後、10％のトリエチルアミンのクロロホルム溶
液中に浸漬して室温で20時間反応させた。クロロ
ホルムで十分洗浄した後、100℃で一夜真空乾燥
した。
一方、陰極にアルミニウム箔を使用し、樹脂封
止して固体電解コンデンサを作成した。このよう
にして、容量1.95μF、tanσ1.5％、もれ電流1.5μA
（50V値）、逆耐電圧100V以上の良好な固体電解
コンデンサが得られた。
実施例 ６
本例は本発明で得られたポリ〔１，３―ナフト
〔２，３―Ｃ〕チオフエン〕が電池材料として有
用であることを示す。即ち、本例では電位走査法
にてアニオンドーパントのドーピング／アンドー
ピングの可逆性及び酸化還元の電位を調べた。
実験セルには対極にリチウム箔を用い、参照極
にはリチウム金属を用いた。電解液は1mol／
濃度の過塩素酸リチウムのプロピレンカーボネー
ト溶液を用いた。電位走査速度を１秒間に10mV
で行なつたところ酸化ピークは3.85V（対Li／
Li+）であり、還元ピークは3.30V（対Li／Li+）
であつた。
酸化還元の繰り返しによる電流効率は、100回
の繰り返しでも良好な効率を得、ほぼ100％であ
つた。第３図に電位走査法で調べたポリナフト
〔２，３―Ｃ〕チオフエンの酸化還元電位と電流
の関係を示す。 [Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel electrically conductive polymer that is extremely stable and exhibits extremely high electrical conductivity upon doping, and more particularly relates to a novel electrically conductive polymer that is extremely stable and exhibits extremely high electrical conductivity through doping. (wherein R 1 and R 2 each independently represent a substituent selected from hydrogen, a hydrocarbon having 1 to 5 carbon atoms, a methoxy group, and a methylthio group) naphtho[2,3-C]thiophene The present invention relates to a method for producing a polymer having a structure. This polymer can be used in the electrical and electronic industry for the production of electrodes, electrochromic display elements, solid capacitors, solar cells, etc. [Conventional technology] In recent years, there has been remarkable progress in reducing the weight, thickness, and size of electrical and electronic devices, and there is a strong desire to make the various elements used in these devices lighter, thinner, and smaller. In addition, there are strong expectations for the emergence of new and better materials. In order to meet these demands or expectations, new conductive polymers have been actively developed. for example,
When polyacetylene is doped with iodine or arsenic pentafluoride, it exhibits a high electrical conductivity of 10 2 to 10 3 s/cm [for example, Synthetic Metals 1(2), 101 (1979/
(1980)] is being considered not only as an electrode material for secondary batteries due to its excellent charge and discharge characteristics, but also as a solar cell material because its light absorption characteristics are similar to those of sunlight. has been done. However, polyacetylene itself has the disadvantage that it is easily oxidized, and doped polyacetylene is also very sensitive to moisture. On the other hand, polythiophene has a conjugated structure similar to that of cis-type polyacetylene, and because of its unique electronic structure containing a sulfur atom, it is not only being considered for use as a conductive material or a battery electrode material, but also as an electrolytic material. Its use as a chromic material is also being considered. For example, A.M.
AMDruy et al. discovered that a polymer obtained by electrochemically polymerizing 2,2'-bithienyl changes color from blue to red in an oxidized state to a reduced state.
It has been reported that this phenomenon is reversible, making it useful as an electrochromic material [J. de Physique].
44(6), C3-595 (1983)]. [Problems to be Solved by the Invention] Some of the present inventors have already discovered that a polymer having an isothianaphthene structure is a compound that is extremely stable even in the air, and that it can be used repeatedly.
It has been found that it can reversibly change color during the process of stable oxidation or reduction, and that it easily exhibits conductivity higher than 10 -2 s/cm by doping (Japanese Patent Application Laid-Open No. 17581-1983). Publication No. and JP-A-61-
Publication No. 12784). As a result of further research, the present inventors found that by further expanding the π-conjugated system of the benzene nucleus of the polymer having the above-mentioned isothianaphthene structure to form a naphthene nucleus, conduction with a lower energy gap was achieved. The present invention has been achieved by discovering that it is possible to make a polyester polymer. [Means and effects for solving the problem] The polymer according to the present invention has a general formula as a repeating unit. (wherein R 1 and R 2 each independently represent a substituent selected from hydrogen, a hydrocarbon having 1 to 5 carbon atoms, a methoxy group, and a methylthio group) naphtho[2,3-C]thiophene structure, and such a polymer can be synthesized by the following polymerization method. (1) General formula below 1,3 - dihydronaphtho [2,3
-C]Thiophene-2-oxide and/or its derivatives are dehydrated and polymerized in a solvent such as polyphosphoric acid to produce poly[1,3-dihydronaphtho[2,3-C]thiophene] and/or its derivatives. Then, this is converted into the desired poly[1,3-naphtho[2,3-
[C]thiophene] and/or its derivatives can be produced. (2) General formula obtained by dehydrating and sublimating the compound represented by the above general formula (a) under reduced pressure and heating (wherein R 1 and R 2 are as defined above) naphtho[2,3-C]thiophene and/or its derivatives as (i) a radical polymerization initiator, an anionic polymerization initiator or a cationic polymerization initiator; Polymerize using an agent,
The obtained poly[1,3-dihydronaphtho(2,3-C)thiophene] and/or its derivatives are dehydrogenated by the method described in (1) to obtain the desired polymer, or (ii) Naphtho [2,
3-C] Thiophene and/or its derivatives are electrochemically polymerized in the presence of a solvent and an electrolyte, or (iii) Naphtho[2,
Poly[1,3-naphtho[2,3
-C]thiophene] and/or its derivatives. When polymerizing the monomer represented by the general formula (a) or (b), the polymerization conditions used may be set according to known methods depending on the respective polymerization method and are not particularly limited. That is, when the monomer represented by general formula (b) is electrochemically polymerized, solid state communication is used to polymerize thiophene, pyrrole, etc.
46(5), 389 (1983) can be applied. At this time, either a constant potential method or a constant current method may be used. Also, the method of Jenekhe et al. of polymerizing various substituted or unsubstituted carbazole compounds during oxidative polymerization in liquid iodine, [Symposium on Order in Polymeric Substances]
Materials), Waltham MA
MA) August 25-26 (1983)] can be applied. In addition, in the case of oxidative polymerization using anhydrous aluminum chloride and cuprous chloride, the method of Kovacic et al. [Macromol. Shin. (Macromol.Syn. 2 , 23 (1966)) can be applied. Furthermore, the obtained poly[1,3-dihydronaphtho[2,3-C]thiophene] and/or its derivatives can be dehydrogenated. To obtain the desired poly[1,3-naphtho[2,3-C]thiophene] and/or its derivatives, iodine, bromine or tritylfluoroborate, dichlorodicyano-p-benzoquinone in the presence or absence of a solvent. This can be easily achieved by using a dehydrogenating agent such as chloranil, tetracyanodimethane, etc.The reaction conditions used for the dehydrogenating reaction vary depending on the type of dehydrogenating agent, the presence or absence of a solvent, etc. Although it cannot be specified, when acetonitrile, chlorobenzene, etc. are used, the reaction may be carried out for 1 hour to 24 hours at a temperature between 0°C and the boiling point of the solvent. Dihydronaphtho [2,3-
[C]thiophene] and/or its derivatives in a mole range of 3 times to 20 times per repeating unit. If the dehydrogenation reaction due to the action of these dehydrogenating agents is not sufficiently carried out, the structure of the dihydro compound remains unreacted in the polymer main chain, causing the conjugated chain to be severed and resulting in a decrease in electrical conductivity. Therefore, it is necessary to allow the reaction to occur sufficiently. Poly[1,3-dihydronaphtho[2,3-C]thiophene] and/or poly[1,3-dihydronaphtho[2,3-C]thiophene] obtained by these methods
or a derivative thereof is obtained doped with an excess of a dehydrogenating agent, and can be easily electrochemically or chemically dedoped as required. Chemical dedoping can be easily accomplished by bringing the polymer into contact with a gas or liquid of ammonia or tertiary amines.
As a method of electrochemical dedoping, Kinto et al. Of Apple. Japan J. of Appl. Physics 22 (7), L412 (1983)]
This can be done according to the method. The monomer compound represented by the general formula (a) according to the present invention can be used, for example, by M. P. Hippopotamus (MPCava) etc. Am. Chem. Sok. (J.Am.Chem.Soc.) 81 ,
4266 (1959) and also M. P. Hippo (MP
Cava) et al. Org. Chem. (J.Org.
Chem.) 36 (25), 3932 (1971). [Effects of the Invention] The polymer according to the present invention obtained as described above not only exhibits extremely high conductivity through doping, but also can undergo repeated oxidation and reduction electrochemically. It has a unique color in its state. Poly[1,3-
Naphtho[2,3-C]thiophene] and/or its derivatives are very interesting polymers because they are colorless and transparent in the oxidized state in a thin film state. Therefore, poly[1,3-naphtho[2,3-C]thiophene] and/or its derivatives according to the present invention are used in the electrical and electronic industries for electrodes, electrochromic display elements, solid capacitors, solar cells, etc. It is clear that it is extremely useful in manufacturing. [Examples] The present invention will be described in more detail below with reference to Examples. In addition, in the following examples, the IR of the polymer
The spectrum is manufactured by JASCO Corporation, type A-3 or manufactured by the same company.
The measurement was performed using an IRA-2 type IR spectrophotometer, and the 1 H-NMR spectrum was measured using a 100MHzR-24B high-resolution NMR spectrometer manufactured by Hitachi, Ltd. The viscosity of the polymer was expressed as logarithmic viscosity (ηinh). In addition, the viscosity ηinh in the examples was determined by the following formula (in the formula, the logarithm represents a natural logarithm). ηinh=(1/C)ln(t-to)/to (where, t: Passage time between the marked lines on the viscometer of the polymer solution (seconds) to: Passage time between the marked lines on the viscometer of the pure solvent Time (seconds) C: Concentration of polymer solution (expressed in g/100ml solvent) Example 1 (1) Poly[1,3-dihydronaphtho[2,3-
Synthesis of [C]thiophene] (i) Dehydration polymerization of 1,3-dihydronaphtho[2,3-C]thiophene-2-oxide in polyphosphoric acid 1,3-dihydronaphtho[2,3-C]thiophene- 2-oxide (R 1 = R 2 in general formula (a)
= H) 2.38g (11.8 mmol) under nitrogen stream
Polyphosphoric acid containing 75% phosphorus pentaphosphide heated to °C
After stirring for 4 hours, the reaction solution was
poured into the water. After filtering and washing the generated precipitate, the solid was placed in 500 ml of 5% diluted ammonia water.
After stirring for 1 hour and separating by filtration, the filtrate residue was thoroughly washed with water until the filtrate became neutral, and then washed with methanol and then acetone. The residue was vacuum dried at 100°C overnight.
1.63 g of light brown polymer was obtained. This polymer was soluble in dimethylsulfoxide chlorobenzene and methylene chloride, partially soluble in tetrahydrofuran and dioxane, and insoluble in methanol and acetone. The viscosity of the polymer in a 0.5% dimethyl sulfoxide solution at 30°C was ηinh=0.102. The IR spectrum of the obtained polymer was as shown in FIG. In addition, the 1 H-NMR of the polymer in deuterated dimethyl sulfoxide solution based on tetramethylsilane is 7~
Naphthalene ring proton at 8ppm, 1 at 4.4ppm,
Dicnal of protons of the methine group of 3-substituted dihydrothiophene appeared, and the integrated intensity ratio of the protons was approximately 6:2. Also, the elemental analysis value is C:
78.5%, H: 4.35% (calculated values are C: 78.26%, H:
4.35%). (ii) Cationic polymerization of naphtho[2,3-C]thiophene 1,3-dihydronaphthothiophene-2-oxide (R 1 =R 2 =H in general formula (a)) 1g (5
After pulverizing and mixing 2 g of neutral alumina in a mortar and filling it into a sublimation device, cooling water was passed through the inner cylinder, and while maintaining the internal temperature at 20 mmHg, the outer cylinder was heated to 175 mmHg.
immersed on an oil bath at °C. After 2 hours, the yellow crystals sublimated and deposited on the gold finger portion of the inner cylinder were transferred to another sublimation device under a nitrogen atmosphere, and then dehydrated again at room temperature under a reduced pressure of 1 mmHg. 450mg obtained
(2.5 mmol) of naphtho[2,3-C]thiophene was dissolved in 5 ml of methylene chloride previously dehydrated and distilled over calcium hydride, cooled to -40°C in a nitrogen atmosphere, and added with 10 volumes of boron trifluoride etherate. % methylene chloride solution was added. The solution immediately turned dark purple and became a viscous solution after 4 hours. The temperature was maintained at -40°C during the polymerization. Thereafter, 1 ml of a 10% methylene chloride solution of triethylamine was added to the polymerization solution to stop the polymerization. At this time, the polymer solution changed from black-purple to light brown. The polymer solution was added to 100 ml of methanol to form a precipitate, and the precipitate was filtered off, washed with methanol and then with acetone, and then vacuum-dried overnight to obtain 380 mg of a dark brown polymer. The viscosity of the polymer in 0.5% dimethyl sulfoxide at 30°C was ηinh=0.156. Moreover, the IR spectrum completely matched that obtained in (i) above. (iii) Radical polymerization of naphtho[2,3-C]thiophene In the same manner as in (ii), 1,3-dihydronaphtho[2,
1 g (5 mmol) of 3-C]thiophene-2-oxide was dehydrated by sublimation to obtain 500 mg (2.72 mmol) of naphtho[2,3-C]thiophene. Put this into a clean polymerization sealed tube purged with nitrogen, and add 5 ml of purified chlorobenzene and 12 mg (5.46 x 10 -2 mmol).
of azobisisovaleronitrile was added, the mixture was immersed in a dry ice-ethanol bath, and then degassed under vacuum. After returning to room temperature, it was recooled and degassed. After repeating this operation five times, the polymerized sealed tube was melt-sealed under vacuum. This sealed tube was polymerized at 60°C for 24 hours. The sealed tube was opened, and the polymer chlorobenzene was added to 100 ml of methanol to precipitate the polymer, which was then filtered, washed with acetone, and dried under vacuum to obtain 260 mg of a light brown polymer. . The viscosity of the obtained polymer in a 0.5% dimethyl sulfoxide solution at 30°C was ηinh=0.07.
The IR spectrum of this product is consistent with that synthesized in (i), and poly[1,3-dihydronaphtho[2,3
-C]Thiophene]. (iv) Anionic polymerization of naphtho[2,3-C]thiophene In the same manner as in (ii), 1,3-dihydronaphtho[2,
3-C] 2 g (9.9 mmol) of thiophene-2-oxide was dehydrated by sublimation, and 1.06 g (5.76 mmol) was obtained.
Naphtho[2,3-C]thiophene was obtained. Add 50ml of this to a magnetic stirrer, reflux condenser, and thermometer.
After purging the inside with nitrogen, add 10 ml of tetrahydrofuran dehydrated and purified over calcium hydride in a conventional manner, and then add n-
Butyllithium n-hexane solution (concentration 10%)
0.2 ml of was added, and the mixture was reacted at 60°C for 24 hours with stirring. This was added to 100 ml of methanol to precipitate the polymer, which was then separated, the filter residue was washed in a conventional manner, and vacuum dried at 100°C overnight to form a light brown polymer.
0.58g was obtained. The IR spectrum (i) matches that of the synthesized poly[1,3-dihydronaphtho[2,3
-C]Thiophene]. The viscosity of the polymer in a 0.5% dimethyl sulfoxide solution at 30°C was ηinh=0.09. (2) Synthesis of poly[1,3-naphtho[2,3-C]thiophene (i) Poly[1,3-dihydronaphtho[2,3-]
Poly[1,3-naphtho[2,3-C]thiophene] obtained by iodine oxidation of C]thiophene
Synthesis (1) - After dissolving 1 g (5.43 mmol) of poly[1,3-dihydronaphtho[2,3-C]thiophene] obtained in (i) in 25 ml of purified chlorobenzene under nitrogen, 6.90 g (27.2 mmol) of iodine was added and refluxed on an oil bath for 4 hours, resulting in a black-purple precipitate. After the precipitate was filtered off, it was thoroughly washed with chlorobenzene and methanol until the color of iodine was no longer observed. Next, the polymer was suspended in a solution consisting of 30 ml of 37% ammonia water and 70 ml of methanol, and
After heating under reflux for an hour under nitrogen, the precipitate was filtered off, thoroughly washed with methanol, and then vacuum-dried at 100° C. overnight to obtain 0.98 g of a black-green polymer powder. The IR spectrum of the polymer is shown in Figure 2. Since the Weilschyutain reaction of this polymer was negative, it contained no halogen, and the elemental analysis results showed that C: 79.06% and H: 3.40% (calculated values C: 79.12% and H: 3.30%). . This polymer was insoluble in common organic solvents. Furthermore, the electrical conductivity σ RT at room temperature of pellets made by pressing this polymer using an IT press was measured using a 4-terminal conductivity meter, and it was found that σ RT = 2.3 × 10 -2 s/cm. The electrical conductivity of the sample exposed to was σ RT =8.2×10 −1 s/cm. Even when the doped polymer was left in the air at room temperature for one week, there was no change in its electrical conductivity. (ii) Poly[1,3-dihydronaphtho[2,3-
Poly[1,3] by dehydrogenation of C]thiophene]
-Synthesis of naphtho[2,3-C]thiophene] The reaction (1)-(i) was repeated to obtain 1.5 g of a polymer with ηinh=0.117. 1 g of this polymer was added under a nitrogen stream.
It was dissolved in 20 ml of purified acetonitrile, and then 8.97 g (27 mmol) of trityl fluoroborate was added to this solution and reacted at 20° C. for 4 hours. During this time, the polymer separated from the solvent as a black precipitate as the reaction progressed from a pale brown homogeneous solution. After filtering the generated precipitate, wash thoroughly with acetonitrile,
The filter residue was then suspended in 30 ml of chloroform and diluted with 10%
10 ml of a chloroform solution of triethylamine was added thereto, and the mixture was stirred at room temperature overnight. The solid was filtered from the solution and dried under vacuum at 100°C overnight. The IR spectrum of the polymer matched that shown in Figure 2, confirming that it was poly[1,3-naphtho[2,3-C]thiophene]. Example 2 Synthesis of poly[1,3-naphtho[2,3-C]thiophene] by electrochemical polymerization method 2.02 g (10 mmol) of 1,3-dihydronaphtho [2,3-
C] 1.06 by dehydrating and sublimating a mixture of thiophene-2-oxide and 2 g of neutral alumina.
g (5.76 mmol) of naphtho[2,3-C]thiophene was obtained. This monomer was placed in an H-shaped tube with a glass filter at 150 mmol/tetra-n.
- Dissolve butylammonium bromide in 20 ml of acetonitrile solution, use a platinum plate as the cathode and an indium tin oxide evaporated glass substrate with a surface resistance value of 15 Ω/□ as the anode, with a distance between the electrodes of 6 cm, manufactured by Hokuto Denki Co., Ltd., with a constant voltage. Electrochemical polymerization was performed using a constant current generator (type HA-301) by applying current for 50 minutes at a constant printing voltage of 2.50. The current value is 0.7mA at the start of polymerization, and the maximum current value is 0.85mA.
At the end of polymerization, the voltage was 0.49 mA. A dark blue film was deposited on the anode by energization. Example 3 Poly[1,3-naphtho[2,
Synthesis of 2.02 g (10 mmol) of 1,3-dihydronaphtho[2,3-C]thiophene-2-oxide and 2.0 g of 1,3-dihydronaphtho[2,3-C]thiophene-2-oxide by the method described in Example 1-(ii). 0.91 by dehydrating and sublimating a mixture of alumina
g (4.95 mmol) of naphtho-[2,3-C]thiophene was obtained. Add this to 22ml of tetrahydrofuran
1.18 g (5.2 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone dissolved in
was added and incubated at room temperature for 1 hour and at 40°C for 2 hours under nitrogen atmosphere.
The reaction was carried out at reflux temperature for 3 hours. After filtering the obtained precipitate, 20 ml of methanol was added six times, and 50 ml of 0.2
Once with methanol solution of normal caustic soda, and then
By washing three times with 50 ml of methanol and then vacuum drying at 100° C. overnight, 0.85 g of a black-green polymer powder was obtained. The IR spectrum of this polymer matched that shown in FIG. The Weilschütaine reaction of this polymer was negative, so it contained no halogen, and elemental analysis showed that C: 79.15%.
H: 3.40% (calculated value C: 79.12%, H: 3.30%). When the conductivity σ RT at room temperature of pellets made by pressing this polymer powder with an IT press was measured using a 4-terminal conductivity meter, σ RT =
It was 2.1×10 -2 s/cm. Example 4 Poly[1,3-naphtho[2,
This shows that 3-C]thiophene is useful as an electrochromic display element material. [Electrochromic material experiment] Using the conductive glass coated with poly[naphtho[2,3-C]thiophene] obtained in Example 2 as the negative electrode and the platinum wire as the positive electrode, 0.16 mol/acetonitrile of lithium perchlorate was used as the negative electrode. When a voltage of 4.50 V was applied in the solution, the polymer thin film changed from deep blue to colorless, and when a voltage of -1.5 V was applied in the opposite direction, it changed from colorless to dark blue. This change can be made reversible by repeated voltage application, and it has been shown that the material is useful as an electrochromic display material. Example 5 This example shows that poly[1,3-naphtho[2,3-C]thiophene] obtained according to the present invention is useful as a material for solid capacitors. Using a 100 μm thick aluminum foil (99.99% purity) as an anode, the surface of the foil was electrochemically etched to give an average pore diameter of 2 μm and a specific surface area of 12 m 2 /g. A thin layer of the dielectric was then applied electrochemically to the etched aluminum foil in a solution of ammonium borate. σinh= obtained in reaction (1)-(i) of Example 1
0.117 polymer is dissolved in 3 ml of purified acetonitrile under a nitrogen stream and applied to the derivative layer,
After repeating vacuum degassing to sufficiently fill the pores with the solution, acetonitrile was dry-upped. Subsequently, it was immersed in an acetonitrile solution of trityl fluoroborate (1 mol/) and reacted at 20°C for 20 hours. The foil was taken out and washed with acetonitrile, then immersed in a 10% triethylamine solution in chloroform and reacted at room temperature for 20 hours. After thorough washing with chloroform, it was vacuum dried at 100°C overnight. On the other hand, a solid electrolytic capacitor was created by using aluminum foil for the cathode and sealing it with resin. In this way, capacitance 1.95μF, tanσ1.5%, leakage current 1.5μA
(50V value), a good solid electrolytic capacitor with a reverse withstand voltage of 100V or more was obtained. Example 6 This example shows that poly[1,3-naphtho[2,3-C]thiophene] obtained according to the present invention is useful as a battery material. That is, in this example, the reversibility of doping/undoping of an anion dopant and the redox potential were investigated using a potential scanning method. In the experimental cell, lithium foil was used as the counter electrode, and lithium metal was used as the reference electrode. Electrolyte is 1mol/
A solution of concentrated lithium perchlorate in propylene carbonate was used. Potential scanning speed 10mV per second
The oxidation peak was 3.85V (vs. Li/
Li + ), and the reduction peak is 3.30V (vs. Li/Li + )
It was hot. The current efficiency obtained by repeating redox was good even after 100 repetitions, and was almost 100%. FIG. 3 shows the relationship between the oxidation-reduction potential and current of polynaphtho[2,3-C]thiophene investigated by the potential scanning method.
第１図は実施例１―(1)―(i)で製造した重合体の
赤外吸収スペクトル図である。
第２図は実施例１―(2)―(i)で製造した重合体の
赤外吸収スペクトル図である。
第３図は実施例６の電池材料試験で得られた重
合体の酸化還元電位と電流との関係を示すチヤー
ト図である。
FIG. 1 is an infrared absorption spectrum diagram of the polymer produced in Example 1-(1)-(i). FIG. 2 is an infrared absorption spectrum diagram of the polymer produced in Example 1-(2)-(i). FIG. 3 is a chart showing the relationship between the redox potential and current of the polymer obtained in the battery material test of Example 6.
Claims (1)
素数１〜５の炭化水素、メトキシ基及びメチルチ
オ基から選ばれた置換基を表わす） で表わされる１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン―２―オキシド及び／又はその誘
導体を、溶媒中で脱水重合させ、次いで得られた
ポリ〔１，３―ジヒドロナフト〔２，３―Ｃ〕チ
オフエン〕及び／又はその誘導体に脱水素剤を作
用させることを特徴とする、くり返し単位として
一般式 （式中、R1及びR2は前に定義した通りである） で表わされるナフト〔２，３―Ｃ〕チオフエン構
造を有する重合体の製造方法。 ２ 一般式 （式中、R1及びR2はそれぞれ独立に水素、炭
素数１〜５の炭化水素、メトキシ基及びメチルチ
オ基から選ばれた置換基を表わす） で表わされる１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン―２―オキシド及び／又はその誘
導体を、減圧加熱下に脱水昇華させて得られる一
般式 （式中、R1及びR2は前に定義した通りである） で表わされるナフト〔２，３―Ｃ〕チオフエン及
び／又はその誘導体を重合開始剤の存在下に重合
させ、得られるポリ〔１，３―ジヒドロナフト
〔２，３―Ｃ〕チオフエン〕及び／又はその誘導
体に脱水素剤を作用させることを特徴とするくり
返し単位として一般式 （式中、R1及びR2は前に定義した通りである） で表わされるナフト〔２，３―Ｃ〕チオフエン構
造を有する重合体の製造方法。 ３ 一般式 （式中、R1及びR2はそれぞれ独立に水素、炭
素数１〜５の炭化水素、メトキシ基及びメチルチ
オ基から選ばれた置換基を表わす） で表わされる１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン―２―オキシド及び／又はその誘
導体を、減圧加熱下に脱水昇華させて得られる一
般式 （式中、R1及びR2は前に定義した通りである） で表わされるナフト〔２，３―Ｃ〕チオフエン及
び／又はその誘導体を溶媒及び電解質の存在下に
電気化学的に重合させることを特徴とする、くり
返し単位として一般式 （式中、R1及びR2は前に定義した通りである） で表わされるナフト〔２，３―Ｃ〕チオフエン構
造を有する重合体の製造方法。 ４ 一般式 （式中、R1及びR2はそれぞれ独立に水素、炭
素数１〜５の炭化水素、メトキシ基及びメチルチ
オ基から選ばれた置換基を表わす） で表わされる１，３―ジヒドロナフト〔２，３―
Ｃ〕チオフエン―２―オキシド及び／又はその誘
導体を、減圧加熱下に脱水昇華させて得られる一
般式 （式中、R1及びR2は前に定義した通りである） で表わされるナフト〔２，３―Ｃ〕チオフエン及
び／又はその誘導体を酸化重合させることを特徴
とする、くり返し単位として一般式 （式中、R1及びR2は前に定義した通りである） で表わされるナフト〔２，３―Ｃ〕チオフエン構
造を有する重合体の製造方法。[Claims] 1. General formula 1,3 - dihydronaphtho [ 2 , 3-
C] Thiophene-2-oxide and/or its derivatives are dehydrated and polymerized in a solvent, and then the obtained poly[1,3-dihydronaphtho[2,3-C]thiophene] and/or its derivatives are subjected to dehydrogenation. A general formula as a repeating unit characterized by the action of an agent. (wherein R 1 and R 2 are as defined above) A method for producing a polymer having a naphtho[2,3-C]thiophene structure. 2 General formula 1,3 - dihydronaphtho [ 2 , 3-
C] General formula obtained by dehydrating and sublimating thiophene-2-oxide and/or its derivatives under reduced pressure and heating (wherein R 1 and R 2 are as defined above) The naphtho[2,3-C]thiophene and/or its derivatives represented by the following formula are polymerized in the presence of a polymerization initiator to obtain a poly[ As a repeating unit characterized by the action of a dehydrogenating agent on 1,3-dihydronaphtho[2,3-C]thiophene] and/or its derivatives, the general formula (wherein R 1 and R 2 are as defined above) A method for producing a polymer having a naphtho[2,3-C]thiophene structure. 3 General formula 1,3 - dihydronaphtho [ 2 , 3-
C] General formula obtained by dehydrating and sublimating thiophene-2-oxide and/or its derivatives under reduced pressure and heating (wherein R 1 and R 2 are as defined above) Electrochemically polymerizing naphtho[2,3-C]thiophene and/or its derivatives in the presence of a solvent and an electrolyte. A general formula as a repeating unit, characterized by (wherein R 1 and R 2 are as defined above) A method for producing a polymer having a naphtho[2,3-C]thiophene structure. 4 General formula 1,3 - dihydronaphtho [ 2 , 3-
C] General formula obtained by dehydrating and sublimating thiophene-2-oxide and/or its derivatives under reduced pressure and heating (wherein R 1 and R 2 are as defined above) As a repeating unit of the general formula (wherein R 1 and R 2 are as defined above) A method for producing a polymer having a naphtho[2,3-C]thiophene structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60094584A JPS61254620A (en) | 1985-05-04 | 1985-05-04 | Polymer having naphtho(2,3-c)thiophene structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60094584A JPS61254620A (en) | 1985-05-04 | 1985-05-04 | Polymer having naphtho(2,3-c)thiophene structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61254620A JPS61254620A (en) | 1986-11-12 |
| JPH0211614B2 true JPH0211614B2 (en) | 1990-03-15 |
Family
ID=14114323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60094584A Granted JPS61254620A (en) | 1985-05-04 | 1985-05-04 | Polymer having naphtho(2,3-c)thiophene structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61254620A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0273826A (en) * | 1988-09-09 | 1990-03-13 | Toyobo Co Ltd | Production of electrically conductive polymer |
| JPH0275625A (en) * | 1988-09-13 | 1990-03-15 | Toyobo Co Ltd | Electrically conductive polymer |
| JP2001006983A (en) * | 1999-06-22 | 2001-01-12 | Showa Denko Kk | Solid electrolytic capacitor and its manufacture |
| WO2018123177A1 (en) * | 2016-12-28 | 2018-07-05 | 昭和電工株式会社 | Method for producing polyisothianaphthene electroconductive polymer |
-
1985
- 1985-05-04 JP JP60094584A patent/JPS61254620A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61254620A (en) | 1986-11-12 |
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